Doped graphitic carbon nitrides, methods of making and uses of the same

ABSTRACT

Carbon-doped graphitic carbon nitride (g-C 3 N 4 ) compositions are synthesized from the chemical precursors melamine, cyanuric acid and barbituric acid. Phosphorus-doped g-C 3 N 4  compositions are synthesized from the chemical precursors melamine, cyanuric acid and etidronic acid. Carbon- and phosphorus-doped g-C 3 N 4  compositions, when in the presence of UV or visible light, can be used in water treatment systems to photocatalytically degrade persistent organic micropollutants such as pharmaceuticals and personal care products (PPCPs), endocrine disrupting compounds (EDCs), pesticides, and herbicides. Carbon- and phosphorus-doped g-C 3 N 4  compositions can also be applied to surfaces of household and public items to kill protozoa, eukaryotic parasites, algal pathogens, bacteria, fungi, prions, viruses, or other microorganisms, preventing the transfer thereof between users.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. provisional application No. 62/295,624, filed Feb. 16, 2016, the contents of which are incorporated by reference herein in its entirety.

FIELD OF TECHNOLOGY

The present application relates doped graphitic carbon nitride (g-C₃N₄) compositions and methods of making such compositions. The present application also relates to the use of doped g-C₃N₄ compositions in water treatment and antimicrobial applications.

BACKGROUND

A growing number of persistent organic micropollutants such as pharmaceuticals and personal care products (PPCPs), endocrine disrupting compounds (EDCs), pesticides, and herbicides are frequently observed in natural and treated water. These contaminants are recalcitrant to conventional water and wastewater treatment and may pose risks to human and ecological systems even at very low concentrations. Persistent and emerging waterborne, foodborne, and airborne pathogens can cause the spread of infectious diseases, and their control is important to protect the public health. Photocatalysis is a promising advanced oxidation process (AOP) for the degradation or mineralization of persistent organic micropollutants and the inactivation of pathogens because it activates O₂ and/or H₂O at ambient conditions to generate reactive oxygen species (ROS; e.g., .OH, O₂ ⁻./HO₂., H₂O₂, and ¹O₂) in situ. Photocatalysis also eliminates the hurdles in the storage, handling, and transportation of oxidants or disinfectants, and potentially uses renewable solar energy or indoor lighting for water purification and antimicrobial applications.

Recently, graphitic carbon nitride (g-C₃N₄) has emerged as a visible-light-responsive photocatalyst with tunable band gaps of 1.8-2.7 eV that allow the harvesting of visible light up to 460-698 nm (potentially utilizing 13-49% of solar energy, though photocatalytic activity may be reduced at a longer wavelength). g-C₃N₄ is made from earth-abundant, inexpensive carbon and nitrogen containing precursors (e.g., urea and melamine), is biocompatible with no reported toxicity, is resistant to photo-corrosion, and remains chemically stable in harsh environments.

Supramolecular preassembly of triazine precursors has become an attractive approach to tailor the properties and reactivity of g-C₃N₄. The supramolecular approach is more environmentally benign and sustainable compared to widely used hard-templating with nanosilica because no toxic or corrosive chemicals are involved (e.g., HF or NH₄HF₂ for the post-removal of silica and pore generation). Cyanuric acid has been applied with melamine because they can interact with each other by forming hydrogen bonds, producing a highly stable supramolecule as the precursor of g-C₃N₄. Cyanuric acid is less thermally stable than melamine and decomposes into gases at an elevated temperature, which may create a porous structure of g-C₃N₄ with an increased surface area and charge separation.

The molecular structure of g-C₃N₄ has also been altered with metal and/or nonmetal dopants, or nanoparticles to improve charge separation and visible-light utilization. Such methodologies are disadvantageous, however, because metal dopants or nanoparticles are more expensive (e.g., noble metal loading) and may leach or be deactivated in a complex environment.

BRIEF SUMMARY OF THE DRAWINGS

The accompanying figures illustrate embodiments and serve to explain principles of the disclosed embodiments. It is to be understood, however, that these figures are presented for purposes of illustration only, and not for defining limits of the present invention.

FIG. 1 is an illustration of the chemical structure of a portion of a graphitic carbon nitride (g-C₃N₄) sheet in accordance with various embodiments of the present disclosure;

FIG. 2 is an illustration of a synthetic procedure for the formation of supramolecule-based, carbon-doped g-C₃N₄ (MCB_(x)) compositions in accordance with various embodiments of the present disclosure;

FIG. 3 is an illustration of a synthetic procedure for the formation of supramolecule-based, phosphorus-doped g-C₃N₄ (MCE_(y)) compositions in accordance with various embodiments of the present disclosure;

FIG. 4 is a block diagram of an exemplary water treatment system according to various aspects of the present disclosure;

FIG. 5 is a graph displaying the spectral irradiance of a xenon lamp (λ>400 nm) for use in photocatalytic processes with g-C₃N₄ compositions in accordance with various embodiments of the present disclosure;

FIG. 6 is an illustration of an undoped g-C₃N₄ sheet employed in electronic structure calculations in accordance with various embodiments of the present disclosure;

FIG. 7 is an illustration of designated sites for the doping of a g-C₃N₄ sheet, the doping sites designated as N₁, N₂, N₃, C₁, C₂, and pore, in accordance with various embodiments of the present disclosure;

FIG. 8 is an illustration of optimized geometries of undoped and doped g-C₃N₄ compositions in accordance with various embodiments of the present disclosure;

FIG. 9 is a graphical display of phenol degradation over time using MCB_(x) (x=0.01-1.9), under simulated visible light irradiation, in accordance with various embodiments of the present disclosure;

FIG. 10 is a graphical display of phenol degradation over time using MCE_(y) (y=0.01-0.5), under simulated visible light irradiation, in accordance with various embodiments of the present disclosure;

FIG. 11 is a graphical display of atrazine degradation over time using MCE_(y) (y=0.01-0.5), under simulated visible light irradiation, in accordance with various embodiments of the present disclosure;

FIG. 12 is a graphical display comparing the photocatalytic degradation rate constants of phenol, atrazine, sulfamethoxazole and carbamazepine using the following g-C₃N₄ compositions: 1) g-C₃N₄ synthesized from urea (U), 2) g-C₃N₄ synthesized from melamine (M), 3) g-C₃N₄ synthesized from melamine and cyanuric acid (MC), and 4) g-C₃N₄ synthesized from melamine, cyanuric acid, and barbituric acid (MCB_(0.07)), in accordance with various embodiments of the present disclosure;

FIG. 13 is a graphical display of photocatalytic rate constants of atrazine degradation using MCB_(0.07) under visible light irradiation over four cycles, in accordance with various embodiments of the present disclosure;

FIG. 14 is an attenuated total reflection-Fourier transform infrared spectroscopic (ATR-FTIR) spectra of freshly prepared and recovered MCB_(0.07) before and after use in an atrazine degradation process in accordance with various embodiments of the present disclosure;

FIG. 15 shows scanning electron microscopic (SEM) images of fresh MCB_(0.07) (left) and MCB_(0.07) recovered after an atrazine degradation process (right) in accordance with various embodiments of the present disclosure;

FIG. 16 is a graphical display of the reactivity inhibition of phenol and atrazine degradation using U and MCB_(0.07) in the presence of various scavengers (10 mM of tert-butyl alcohol as a .OH scavenger, 10 mM of ammonium oxalate as a hole scavenger, and 10 mM of L-histidine as a ¹O₂ scavenger) in accordance with various embodiments of the present disclosure;

FIG. 17 is a graphical display of the reactivity inhibition of phenol degradation using U in the presence of various scavengers (10 mM of tert-butyl alcohol as a .OH scavenger, 10 mM of ammonium oxalate as a hole scavenger, and 10 mM of L-histidine as a ¹O₂ scavenger, 2 U/mL of superoxide dismutase as a O₂ ⁻. scavenger, and 200 U/mL of catalase as a H₂O₂ scavenger) in accordance with various embodiments of the present disclosure;

FIG. 18 shows graphical displays of atrazine degradation using (a) freshly prepared MCB_(0.07) suspension in simulated water samples, (b) 24 hour-aged MCB_(0.07) suspension in simulated water samples, (c) freshly prepared MCB_(0.07) suspension in real water samples (raw or (partially) treated water and wastewater from plants), and (d) 24 hour-aged MCB_(0.07) suspension in real water samples (raw or (partially) treated water and wastewater from plants) under simulated visible sunlight irradiation (xenon lamp, λ>400 nm) in accordance with various embodiments of the present disclosure;

FIG. 19 is a graphical display of E. coli disinfection over time using g-C₃N₄ in accordance with various embodiments of the present disclosure;

FIG. 20 shows confocal laser scanning microscopic images of S. epidermidis biofilms developed on the surface of g-C₃N₄ coupons in the dark (left) and under visible light (right) in accordance with various embodiments of the present disclosure;

FIG. 21 shows optical coherence tomographic (OCT) images of S. epidermidis biofilms developed on the surface of g-C₃N₄ coupons in the dark (left) and under visible light (right) in accordance with various embodiments of the present disclosure;

FIG. 22 shows powder X-ray diffraction (XRD) patterns of different g-C₃N₄ compositions (U, M, MC, and MCB_(0.07); a.u. represents arbitrary units) in accordance with various embodiments of the present disclosure;

FIG. 23 shows ATR-FTIR spectra of different g-C₃N₄ compositions (U, M, MC, and MCB_(0.07)) in accordance with various embodiments of the present disclosure;

FIG. 24 shows an SEM image and a transmission electron microscopic (TEM) image (inset) of a g-C₃N₄ composition formed from urea (U), and further shows a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of U in accordance with various embodiments of the present disclosure;

FIG. 25 shows an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from melamine (M), and further shows a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of M in accordance with various embodiments of the present disclosure;

FIG. 26 shows an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from melamine and cyanuric acid (MC), and further shows a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of MC in accordance with various embodiments of the present disclosure;

FIG. 27 shows an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from melamine, cyanuric acid, and barbituric acid (MCB_(0.07)), and further shows a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of MCB_(0.07) in accordance with various embodiments of the present disclosure;

FIG. 28 shows SEM images of MCB_(0.07) prepared in ethanol (a) and water (b) in accordance with various embodiments of the present disclosure;

FIG. 29 is a graphical display of band gap properties of different g-C₃N₄ compositions in accordance with various embodiments of the present disclosure;

FIG. 30 is a graphical display of optical absorbance of different g-C₃N₄ composition suspensions (1 g/L of U, M, MC, and MCB_(0.07) in 1 mM phosphate buffer, pH 7.3) in accordance with various embodiments of the present disclosure; and

FIG. 31 is a graphical display of photoluminescence spectra of different g-C₃N₄ compositions (U, M, MC, and MCB_(0.07); a.u. represents arbitrary units) in accordance with various embodiments of the present disclosure.

DETAILED DESCRIPTION

Exemplary, non-limiting embodiments of the present application will now be described with references to the above-mentioned figures. Particularly, embodiments of the application comprise parts or method steps that are similar or identical to each other. These parts or method steps are thus denoted with similar or identical names or reference numerals. Description of these relevant parts of method steps is hereby incorporated by reference, wherever relevant or appropriate.

As used throughout, ranges are used as shorthand for describing each and every value that is within the range. Any value within the range can be selected as the terminus of the range. Unless otherwise specified, all percentages and amounts expressed herein and elsewhere in the specification should be understood to refer to percentages by weight.

For the purposes of this specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term “about.” The use of the term “about” applies to all numeric values, whether or not explicitly indicated. This term generally refers to a range of numbers that one of ordinary skill in the art would consider as a reasonable amount of deviation to the recited numeric values (i.e., having the equivalent function or result). For example, this term can be construed as including a deviation of ±10 percent, alternatively ±5 percent, and alternatively ±1 percent of the given numeric value provided such a deviation does not alter the end function or result of the value. Accordingly, unless indicated to the contrary, the numerical parameters set forth in this specification and attached claims are approximations that can vary depending upon the desired properties sought to be obtained by the present invention.

It is noted that, as used in this specification and the appended claims, the singular forms “a,” “an,” and “the,” include plural references unless expressly and unequivocally limited to one referent. As used herein, the term “include” and its grammatical variants are intended to be non-limiting, such that recitation of items in a list is not to the exclusion of other like items that can be substituted or added to the listed items. For example, as used in this specification and the following claims, the terms “comprise” (as well as forms, derivatives, or variations thereof, such as “comprising” and “comprises”), “include” (as well as forms, derivatives, or variations thereof, such as “including” and “includes”) and “has” (as well as forms, derivatives, or variations thereof, such as “having” and “have”) are inclusive (i.e., open-ended) and do not exclude additional elements or steps. Accordingly, these terms are intended to not only cover the recited element(s) or step(s), but may also include other elements or steps not expressly recited. Furthermore, as used herein, the use of the terms “a” or “an” when used in conjunction with an element may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.” Therefore, an element preceded by “a” or “an” does not, without more constraints, preclude the existence of additional identical elements.

For the purposes of this specification and appended claims, the term “coupled” refers to the linking or connection of two objects. The coupling can be permanent or reversible. The coupling can be direct or indirect. An indirect coupling includes connecting two objects through one or more intermediary objects. The term “substantially” refers to an element essentially conforming to the particular dimension, shape or other word that substantially modifies, such that the component need not be exact. For example, substantially cylindrical means that the object resembles a cylinder, but can have one or more deviations from a true cylinder.

FIG. 1 is an illustration of the chemical structure of graphitic carbon nitride (g-C₃N₄). g-C₃N₄ as shown in FIG. 1 can be synthesized by, for example, heating a powder of any of urea, melamine, dicyandiamide, or thiourea at elevated temperatures for a predetermined period of time, followed by cooling to room temperature. g-C₃N₄ is in the form of a two-dimensional sheet and characterized by tri-s-triazine (C₆N₇) units, as elementary building blocks, and a pore bounded by three tri-s-triazine units. In some instances, g-C₃N₄ can also be formed from a mixture of melamine and cyanuric acid.

According to various aspect of the present disclosure, carbon (C)-doped supramolecule-based g-C₃N₄ (MCB_(x)) compositions, described herein, can be used to degrade and/or decompose persistent organic micropollutants such as PPCPs, EDCs, pesticides, and herbicides that are frequently observed in natural and treated water. Generally, MCB_(x) compositions can be made by formation of a supramolecular complex from predetermined amounts of the precursors melamine, cyanuric acid, and barbituric acid, followed by thermal polycondensation, as illustrated in FIG. 2. To synthesize MCB_(x) compositions, the following general methodology can be utilized. First, predetermined amounts of melamine, cyanuric acid, and barbituric acid are dispersed in a solvent to form a suspension. The solvent can be, for example, an alcohol such as methanol or ethanol, water, chlorinated solvents such as chloroform or methylene chloride, acetone, an ether such as diethyl or diphenyl ether, and aldehyde, a ketone, any combination thereof, or any other suitable solvent or solvent system. The suspension can then be stirred and agitated for a period of time suitable for the suspension to become substantially homogeneous. Agitation can be, for example, shaking, ultrasonication in a bath or using a probe, or any other suitable agitation process known to one of ordinary skill in the art. The substantially homogeneous suspension can then be subjected to elevated temperature to remove the solvent and to form the supramolecular complex. The dried supramolecular complex can then be placed in a chemically and thermally inert container, such as an alumina or ceramic crucible, and heated to a temperature sufficient to form the final MCB_(x) composition. The temperature used for formation of the final MCB_(x) composition can range from about 450° C. to about 600° C., alternatively about 500° C. to about 600° C., and alternatively about 550° C.

MCB_(x) compositions can be synthesized from a precursor mixture comprising about 50 wt % melamine, about 2.5-49.75 wt % cyanuric acid, and about 0.25-47.5 wt % barbituric acid. For example, preparation of MCB_(x) on a four gram scale can utilize 2 grams of melamine, 0.1 to 1.99 grams of cyanuric acid and 0.01 to 1.9 grams of barbituric acid. In some instances, on a four gram scale, 0.01 to 0.1 grams of barbituric acid is used. As described herein, a MCB_(x) composition formed from, for example, 2 grams of melamine, 1.93 grams of cyanuric acid, and 0.07 grams of barbituric acid is named as “MCB_(0.07).” One of ordinary skill in the art can readily appreciate that more or less MCB_(x) can be produced by scaling the above described values.

The addition of barbituric acid to melamine and cyanuric acid can lead to C-doped g-C₃N₄ compositions via substitution of one or more nitrogen atoms within a tri-s-triazine unit, or via substitution of nitrogen atoms linking tri-s-triazine units together, with a carbon atom (FIG. 2). MCB_(x) compositions according to the present disclosure are substantially mesoporous (i.e. having pores with diameters ranging from about 2 to 50 nm) with surface areas ranging from about 70 m²/g to about 100 m²/g. MCB_(x) compositions according to the present disclosure may also have pore volumes ranging from about 0.5 cm³/g to about 0.8 cm³/g. MCB_(x) compositions according to the present disclosure may also have carbon to nitrogen (C/N) mass ratios ranging from about 0.60 to about 0.70.

According to various aspects of the present disclosure, phosphorus (P)-doped supramolecule-based g-C₃N₄ (MCE_(y)) compositions, described herein, can be used to degrade and/or decompose persistent organic micropollutants such as PPCPs, EDCs, pesticides, and herbicides that are frequently observed in natural and treated water. Generally, MCE_(y) compositions can be made by formation of a supramolecular complex from predetermined amounts of the precursors melamine, cyanuric acid, and etidronic acid, followed by thermal polycondensation, as illustrated in FIG. 3. To synthesize MCE_(y) compositions, the following general methodology can be utilized. First, predetermined amounts of melamine, cyanuric acid, and etidronic acid are dispersed in a solvent to form a suspension. The solvent can be, for example, an alcohol such as methanol or ethanol, water, chlorinated solvents such as chloroform or methylene chloride, acetone, an ether such as diethyl or diphenyl ether, and aldehyde, a ketone, any combination thereof, or any other suitable solvent or solvent system. The suspension can then be stirred and agitated for a period of time suitable for the suspension to become substantially homogeneous. Agitation can be, for example, shaking, ultrasonication in a bath or using a probe, or any other suitable agitation process known to one of ordinary skill in the art. The substantially homogeneous suspension can then be subjected to elevated temperature to remove the solvent and to form the supramolecular complex. The dried supramolecular complex can then be placed in a chemically and thermally inert container, such as an alumina or ceramic crucible, and heated to a temperature sufficient to form the final MCE_(y) composition. The temperature used for formation of the final MCE_(y) composition can range from about 450° C. to about 600° C., alternatively about 500° C. to about 600° C., and alternatively about 550° C.

MCE_(y) compositions can be synthesized from a precursor mixture comprising about 50 wt % melamine, about 37.5-49.75 wt % cyanuric acid, and about 0.25-12.5 wt % etidronic acid. For example, preparation of MCE_(y) on a four gram scale can utilize 2 grams of melamine, 1.5 to 1.99 grams of cyanuric acid and 0.01 to 0.5 grams of etidronic acid. In some instances, on a four gram scale, 0.01 to 0.1 grams of etidronic acid is used. As described herein, a MCE_(y) composition formed from, for example, 2 grams of melamine, 1.97 grams of cyanuric acid, and 0.03 grams of etidronic acid is named as “MCE_(0.03).” One of ordinary skill in the art can readily appreciate that more or less MCE_(y) can be produced by scaling the above described values.

The addition of etidronic acid to melamine and cyanuric acid can lead to P-doped g-C₃N₄ compositions via substitution of one or more nitrogen or carbon atoms within a tri-s-triazine unit, and/or via substitution of nitrogen atoms linking tri-s-triazine units together with a phosphorus atom. In some instances, the addition of etidronic acid to melamine and cyanuric acid can lead to P-doped g-C₃N₄ compositions wherein phosphorus atoms chelate in a bidentate fashion to nitrogen atoms oriented toward the pore (FIG. 3). MCE_(y) compositions according to the present disclosure are substantially mesoporous (i.e. having pores with diameters ranging from about 2 to 50 nm) with surface areas ranging from about 70 m²/g to about 100 m²/g. MCE_(y) compositions according to the present disclosure may also have pore volumes ranging from about 0.5 cm³/g to about 0.8 cm³/g.

In some instances, computational quantum mechanical modelling methods such as, but not limited to density functional theory (DFT), time-dependent density functional theory (TDDFT), chemical or molecular dynamics, semi-empirical and empirical methods, and ab initio methods can be used to rationally design MCB_(x) and MCE_(y) compositions to have thermodynamically stable structures, suitable charge separation, and suitable energy levels of conduction and valence bands to promote photocatalytic oxidation.

In some instances, the presently described MCB_(x) and MCE_(y) compositions can be used in the presence of ultraviolet (UV) or visible light as a photocatalyst in water treatment applications. Specifically, MCB_(x) and MCE_(y) compositions can be used to degrade persistent organic micropollutants such as PPCPs, EDCs, pesticides, and herbicides which are frequently observed in natural and treated water. In general, the target pollutants can be anything that degrades or decomposes in the presence of ROS (e.g., —OH, O₂ ⁻./HO₂., H₂O₂, and ¹O₂) in situ. In the present disclosure, phenol, atrazine, sulfamethoxazole, and carbamazepine are discussed as target pollutants/contaminants. One of ordinary skill in the art, however, can readily appreciate that MCB_(x) and MCE_(y) compositions can be used to degrade or decompose target pollutants/contaminants having chemical structures similar to such compounds.

In some instances, MCB_(x) and MCE_(y) compositions can be used to degrade aliphatic or aromatic hydrocarbons. In other instances, MCB_(x) and MCE_(y) compositions can be used to degrade aliphatic or aromatic alcohols. In yet other instances, MCB_(x) and MCE_(y) compositions can be used to degrade substituted or unsubstituted triazines. In yet other instances, MCB_(x) and MCE_(y) compositions can be used to degrade substituted or unsubstituted oxazoles or oxazodines. In yet other instances, MCB_(x) and MCE_(y) compositions can be used to degrade substituted or unsubstituted pyrroles, pyridines, purines, and pyrimidines. In yet other instances, MCB_(x) and MCE_(y) compositions can be used to degrade substituted or unsubstituted azepines. In yet other instances, MCB_(x) and MCE_(y) compositions can be used to degrade aldehydes, ketones, esters and carboxylic acids. In yet other instances, MCB_(x) and MCE_(y) compositions can be used to degrade amines, imines, amides, and sulfonamides. While specific examples of compounds which can be degraded by MCB_(x) and MCE_(y) compositions are provided above, one of ordinary skill in the art can readily appreciate that the MCB_(x) and MCE_(y) compositions disclosed herein can be used to degrade any compounds which are reactive to ROS (e.g., .OH, O₂ ⁻./HO₂., H₂O₂, and ¹O₂).

In some instances, where a MCB_(x) or MCE_(y) composition is used as a photocatalyst in water treatment applications, the MCB_(x) or MCE_(y) composition can be formed into any one of a bulk powder, a porous brick or sponge-like material, a wafer, a film, or any other suitable shape. The shaped MCB_(x) or MCE_(y) composition can be placed in a cartridge, piping, or similar containment means. The cartridge or similar containment means can have a fluid inlet for entry of contaminated water or fluid therein and a fluid outlet for the water or fluid to exit after degradation of the contaminant(s) by the MCB_(x) or MCE_(y) composition. The cartridge, piping or similar containment means should be transparent or substantially transparent to allow for the passage or UV or visible light to pass therethrough. In some instances, thin films, sheets wafers or coupons can be formed by subjecting a bulk powder of a MCB_(x) or MCE_(y) composition, or a combination of MCB_(x) and MCE_(y) compositions, to high pressure, such as a hydraulic or pneumatic press. In other instances, a bulk powder of a MCB_(x) or MCE_(y) composition, or a combination of MCB_(x) and MCE_(y) compositions, can be formed into a shaped porous brick or sponge-like material using a tablet press or similar device. The tablet press or similar device can have any suitable dimensions to make shaped porous bricks or sponge-like materials having dimensions for small to industrial scale water treatment applications.

FIG. 4 is a block diagram of an exemplary water treatment system according to various aspects of the present disclosure. The water treatment system 400 includes a water purification assembly 410 and a contaminated water source 420. The water purification assembly 410 includes a top surface 411, a transparent plate 413, a contaminated water stream 414 having a contaminated water inlet (not shown) and a concentrated contaminated water outlet (not shown), a membrane 415 including a MCB_(x) composition and/or a MCE_(y) composition, and purified water stream 416 having a purified water outlet (not shown). The top surface 411 includes an aperture 412 for the transmission of UV or visible light therethrough to irradiate the MCB_(x) composition and/or MCE_(y) composition-containing membrane 415 for the production of ROS. Contaminated water is transmitted from the contaminated water source 420 to the contaminated water stream 414, is purified by the membrane 415, and then enters the purified water stream 416. A pressurized gas source 430 is fluidically coupled with the contaminated water source 420 to assist in transmission of the contaminated water from the contaminated water source 420 to the contaminated water stream 414. The purified water outlet of the purified water stream 416 is fluidically coupled with an inlet (not shown) of a purified water container 440. The remaining contaminated water, now concentrated, is transmitted from the contaminated water stream 414, through the concentrated contaminated water outlet, to an inlet (not shown) of a water bath cooler 470 with the aid of a pump 460. The contaminated water may then re-enter the contaminated water source 420 from the water bath cooler 470, for further purification. A pressure vent valve 450 may be disposed between the contaminated water stream 414 and the pump 460. While the water treatment system 400 of FIG. 4 includes numerous components, one of ordinary skill in the art can readily appreciate that other components can be added to the water treatment system 400 without imparting from the scope of the present disclosure.

In some instances, the presently described MCB_(x) and MCE_(y) compositions can be used in the presence of UV or visible light as a photocatalyst in antimicrobial applications. Specifically, MCB_(x) and MCE_(y) compositions can be used to inactivate protozoa, eukaryotic parasites, algal pathogens, bacteria, fungi, prions, viruses, or other microorganisms which are frequently observed in water, air, food, or on any surfaces. In general, MCB_(x) and MCE_(y) compositions can be used against any protozoa, eukaryotic parasites, algal pathogens, bacteria, fungi, prions, viruses, or other microorganism that inactivates, degrades or decomposes in the presence of ROS (e.g., .OH, O₂ ⁻/HO₂., H₂O₂, and ¹O₂) in situ.

To inactivate protozoa, eukaryotic parasites, algal pathogens, bacteria, fungi, prions, viruses or other microorganisms, compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to any surface based on desired use. For instance, compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to surfaces, including portions gripped by a hand of a user, of kitchen counter-tops, cutting boards, cabinet, drawer or appliance handles or knobs to degrade potentially dangerous bacteria or viruses which may be transferred thereon during the preparation of meals or foodstuffs. In other instances, compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to the surface of food processing machines and food packages. In other instances, compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to the surfaces of furniture such as, for example desks, tables, lighting fixtures (for example, lamps), and so on to degrade communicable viruses or bacteria that may be transferred thereon by users, preventing the spread of such communicable viruses or bacteria to other users. In yet other instances, compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to the surfaces of light or power switches. In yet other instances, the compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to surface of, or impregnated in, woven textiles such as, but not limited to, yarns, fabrics, articles of clothing, medical or laboratory garments, drapery, and so on. In yet other instances, compositions comprising MCB_(x) and/or MCE_(y) compositions can be applied to any surface of interest in hospitals, doctors' or dentists' offices, rehabilitation facilities, hospice care facilities, etc. where the chances of the spread of communicable viruses or bacteria is especially high.

In some instances, MCB_(x) and MCE_(y) compositions may be used to degrade or inactivate bacteria such as, but not limited to, E. coli, staphylococcal species such as S. epidermidis, S. haemolyticus and S. aureus, Legionella species such as Legionella pneumophila, Vibrio cholera, Campylobacter, Brucella, Clostridium perfringens, Listeria, Salmonella, and Shigella.

In some instances, MCB_(x) and MCE_(y) compositions may be used to degrade or inactivate viruses such as, but not limited to, norovirus, rotavirus, adenovirus, and strains of influenza.

In some instances, MCB_(x) and MCE_(y) compositions may be used to degrade or inactivate protozoa such as, but not limited to, Cryptosporidium parvum, Giardia lamblia, and Naegleria fowleri.

In some instances, MCB_(x) and/or MCE_(y) compositions can be applied to surfaces with the aid of an adhesive. In such instances, an adhesive layer can first be disposed on a surface of an article and a layer of a MCB_(x) composition, a MCE_(y) composition, or a combination thereof can be disposed on the adhesive layer. In some instances, the MCB_(x) composition, the MCE_(y) composition, or combination thereof can be disposed upon the adhesive layer as a bulk powder using a powder coating method, a spray coating method or any other suitable powder application method known to one of ordinary skill the art. In other instances, a MCB_(x) composition, a MCE_(y) composition, or a combination thereof can first be formed into a film or sheet as described above and the film or sheet can be applied on the adhesive layer using a roll-to-roll coating technique, a lamination technique such as heated roll lamination or cold roll lamination, or any other suitable film or sheet application technique known to one of ordinary skill in the art. Adhesives suitable for application of a MCB_(x) composition, a MCE_(y) composition, or a combination thereof to a surface of an article can include, but is not limited to epoxies, polyurethanes, polychloroprene, polyamides, polyimides, polyacrylates, natural rubbers, shellac, polyvinyl compounds (such as polyvinyl acetate, alcohol, butyral, chloride, etc.), polyethylene, polypropylene, or any other suitable adhesive known to one of ordinary skill in the art.

In other instances, MCB_(x) and/or MCE_(y) compositions can be dispersed in a solvent to form a MCB_(x) and/or MCE_(y) containing suspension. The suspension can then be applied to a surface of an article and subsequently dried. Such methods can be, but are not limited to, dip-coating spin-coating, slit-coating, drop-casting, doctor blading, and inkjet printing, or any other suitable suspension method known to one of ordinary skill in the art.

In some instances, other additives, such as binders, rheology modifiers, and the like, can be incorporated into the MCB_(x) or MCE_(y) solution to modify its coating properties. Any additives added, however, should be substantially transparent to allow for the passage of UV or visible light therethrough to prevent deleterious effects to the photocatalytic efficiency of the MCB_(x) or MCE_(y) compositions. Furthermore, any adhesive or additive(s) used should be non-reactive or substantially non-reactive in the presence of ROS to prevent the degradation of the adhesive or additive(s) and loss of the MCB_(x) or MCE_(y) compositions from the surface by, for example, delamination.

EXAMPLES

The following examples are intended to be illustrative only, and are not intended to be, nor should they be construed as, limiting in any way of the scope of the present disclosure.

I. Materials and Methods Reagents

All chemicals were at least reagent grade and used as received. The synthesis of g-C₃N₄ involved urea (Sigma-Aldrich, 98%), melamine (Acros Organic, 99+%), cyanuric acid (Sigma-Aldrich, 98%), barbituric acid (Sigma-Aldrich, 99%), etidronic acid monohydrate (Sigma-Aldrich, 95+%), and ethanol (Sigma-Aldrich, 99.5%). A buffer solution of 1 mM potassium phosphate monobasic (Fisher Scientific, 99.3%) was adjusted to pH 7.3 and used in photocatalytic experiments. Phenol (Sigma-Aldrich, 99+%), atrazine (Sigma-Aldrich, 98.8%), carbamazepine (Sigma-Aldrich, 98+%), and sulfamethoxazole (Sigma-Aldrich, 99+%) were used as probe contaminants in photocatalytic studies. Potassium nitrate (Fisher Scientific, 99.9%), humic acid sodium salt (Sigma-Aldrich), magnesium chloride (Fisher Scientific, 99.4%), calcium chloride dihydrate (Fisher Scientific, 74.3%), and sodium hydrosulfide hydrate (Sigma-Aldrich, NaHS 60+%) were selected as representative natural water constituents or foulants for photocatalytic reactions. Ammonium oxalate (Sigma-Aldrich, 99+%), tert-butyl alcohol (Sigma-Aldrich, 99+%), superoxide dismutase (from bovine erythrocytes, Sigma-Aldrich, >3,000 units/mg of protein), catalase (from bovine liver, lyophilized powder, Sigma-Aldrich, 2,000-5,000 units/mg of protein), and L-histidine (Sigma-Aldrich, 99+%) were selected as scavengers for oxidative species in photocatalytic reactions. The eluents for high performance liquid chromatographic (HPLC) analyses of pollutants consisted of sodium acetate (Sigma-Aldrich, anhydrous), potassium phosphate monobasic (Fisher Scientific, 99.3%), acetonitrile (ACN) (Fisher Scientific, 99.9%), and methanol (Sigma-Aldrich, 99.9%). All solutions were prepared in ultrapure water (Millipore, Milli-Q, 18.2 MW cm).

Density Functional Theory (DFT) Simulations

Electronic structure calculations were conducted using DFT as implemented in the CP2K suite. An initial cell relaxation was performed with the Perdew-Burke-Ernzerhof (PBE) density functional, a moderately-sized double-zeta valence polarized (DZVP) basis set, and Goedecker-Teter-Hutter (GTH) pseudopotentials (grid cutoff of 300 Ry), in a hybrid Gaussian-plane wave (GPW) framework. This optimized cell geometry was then used to define subsequent relaxations for undoped and doped materials via the range-separated, hybrid Heyd-Scuseria-Ernzerhof 06 (HSE06) functional. Energy shifts due to solvation were quantified by performing a reference calculation on undoped g-C₃N₄ using an implicit model.

All structures with nitrogen site substitutions were assumed to be uncharged, while interstitially doped systems and those with dopants at carbon sites were assigned a charge of +1. The relative stability of each dopant family was determined by comparing geometries optimized using undoped g-C₃N₄ cell parameters, excluding the nitrogen to carbon substitutions which used the average of optimized cell parameters for that series of dopants.

Synthesis of g-C₃N₄, Carbon Doped g-C₃N₄, and Phosphorus-Doped g-C₃N₄

The conventional g-C₃N₄ samples were synthesized from urea (U) or melamine (M). 10 g of urea or melamine powder was put into an alumina crucible with a cover (not sealed), heated at a rate of 2.3° C./min and maintained at 550° C. for 4 h in a muffle furnace, and then cooled down naturally.

The supramolecule-based g-C₃N₄ samples without non-metal doping were synthesized from melamine and cyanuric acid (MC, mass ratio 1:1).

Carbon-doped, supramolecule-based g-C₃N₄ samples (MCB_(x)), were synthesized from melamine, cyanuric acid, and barbituric acid with different mass ratios (i.e., 2 g of melamine, (2-x) g of cyanuric acid, and x g of barbituric acid; x=0-1.9).

Phosphorus-doped, supramolecule-based g-C₃N₄ samples (MCE_(y)), were synthesized from melamine, cyanuric acid, and etidronic acid with different mass ratios (i.e., 2 g of melamine, (2-y) g of cyanuric acid, and y g of etidronic acid; y=0-0.5).

The synthetic procedure of the MC, MCB_(x), and MCE_(y) samples was as follows. Precursors were first dispersed in 40 mL of ethanol to form suspension. The suspension was next stirred at ambient temperature for 3 h, followed by sonication (Elamsonic P, 37 kHz, 100 W) at room temperature for an additional 3 h. The suspension was then dried on a hot plate at 70° C. until no obvious liquid was found, and white supramolecular aggregates were formed. Finally, the dried supramolecular aggregates were put into an alumina crucible with a cover (not sealed), heated at a rate of 2.3° C./min and maintained at 550° C. for 4 h in a muffle furnace, and cooled down naturally.

Characterization of g-C₃N₄ Carbon-Doped g-C₃N₄ and Phosphorus Doped g-C₃N₄

The crystal phase of g-C₃N₄ was determined by X-ray powder diffraction (XRD) analyses on a Rigaku Miniflex+ diffractometer with Cu Kα radiation.

Sample morphologies were characterized with a scanning electron microscope (SEM, JEOL 6700F) and a transmission electron microscope (TEM, Philips CM300 FEG). For SEM, g-C₃N₄ samples dispersed in ethanol were cast and dried on a sample stub, and SEM micrographs were collected at 10 kV with a secondary electron detector. For TEM, g-C₃N₄ samples dispersed in ethanol were also cast and dried on a Cu grid with a carbon support, and TEM images were collected at 300 kV. The elemental distribution of MCE_(y) was characterized by SEM-energy dispersive spectroscopy (EDS) (SEM, TESCAN MIRA3 FEI; EDS, TEAM Octane SSD) at an accelerating voltage of 20 kV.

Surface properties were investigated by X-Ray photoelectron spectroscopy (XPS). A PHI 5600 system was used for analysis under UHV conditions (pressure <10⁻⁸ Torr). An Mg Kα source (1253.6 eV) was utilized, and ejected photoelectrons were measured with a hemispherical energy analyzer operating at 58.7 eV constant pass-energy. Peak positions were referenced to C1s, 284.5 eV, and CasaXPS was used to determine chemical composition and atomic concentrations at the surface (up to ca. 10 nm).

Attenuated total reflectance-Fourier transform infrared spectroscopic (ATR-FTIR) spectra were collected using a Nicolet 6700 spectrometer from 4000-525 cm⁻¹ (32 scans at 4 cm⁻¹ resolution). Spectra were peak normalized by the C—N asymmetric stretch at 1231 cm⁻¹, a region present in every sample tested with relative invariant spectral intensity.

Brunauer-Emmitt-Teller (BET) surface area and porosity analyses were performed by N₂ adsorption/desorption using a Micromeritics Tri Star 3000. Isotherm adsorption data for P₀/P was recorded from 0.06-0.989. The volume of micropores was determined by t-plot analysis and the volume of mesopores was determined by BJH analysis. Samples were degassed at 140° C. for 12 h under dynamic vacuum (10⁻³ Torr) prior to analysis.

Bulk carbon, hydrogen, and nitrogen were analyzed on Model CE 440 CHN Analyzer. The capsule containing g-C₃N₄ samples was injected into a high temperature (1000° C.) furnace and combusted in pure O₂ under static conditions. To ensure the complete combustion, a dynamic burst of O₂ was added at the end of the combustion period. The resulting combustion product contained CO₂, H₂O, and N₂/NO_(x), and it next passed over Cu to scrub excess O₂ and reduce NO_(x) to N₂. After scrubbing, the gases entered a mixing volume chamber to ensure a homogenous mixture at constant temperature and pressure, and were detected by high-precision thermal conductivity detectors. An H₂O trap and a CO₂ trap were used between the detectors, and the differential signal before and after the trap was proportional to the H₂O concentration and CO₂ concentration. Finally, N₂ was measured against a He reference.

Optical absorbance spectra of the photocatalysts and their band gap were determined by a Thermo Scientific Evolution 300 UV-vis spectrophotometer with a Praying Mantis diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) accessory. The absorbance of g-C₃N₄ samples irradiated by light over a wavelength scan from 200 to 800 nm was measured, and the value was then converted into reflectance by equation 1:

A=log(1/R)  (1)

where A is the measured absorbance and R is the reflectance. The function α, representative of optical absorption, which is equivalent to adsorption coefficient divided by scattering coefficient for g-C₃N₄, was calculated from the Kubelka-Munk formula:

α=(1−R)²/2R  (2)

The band gap was obtained by extrapolating the linear portion of (αhv)^(1/2) versus photon-energy plots at (αhv)^(1/2)=0, h is Planck's constant (4.14×10⁻⁵ eV·s), v is the frequency of photons which can be obtained by dividing c, the speed of light (3.0×10⁸ m/s) by λ, the photon's wavelength.

Photoluminescence (PL) spectra were obtained from a home-made apparatus based on a Thermo Nicolet Nexus 670 rapid scan FTIR spectrometer. The PL spectra of the samples were obtained using a 354 nm diode pumped solid state laser from Teem Photonics as excitation source. The intensity on the samples was 30 μW focused to a spot of 100 μm in diameter. The emitted fluorescence was focused to a 300 mm path length monochromator and collected by a thermoelectrically-cooled charge-coupled device (CCD) camera, both from Princeton Instruments. A long wavelength pass filter cutting at 420 nm was used to block the laser light into the monochromator.

Zeta potential and hydrodynamic diameter of g-C₃N₄ aqueous suspensions were determined using folded capillary cells (DTS 1061, Malvern) on a Zetasizer Nano ZS instrument (Malvern, ZEN3600). The temperature was maintained at 25° C., and the scattering angle was 173° from the incident laser beam.

Ultraviolet-visible (UV-vis) spectra of g-C₃N₄ aqueous suspension was obtained on a Thermo Scientific Evolution 201PC spectrophotometer. The absorption spectra of the catalyst suspension were measured in the region of 200 to 800 nm with at a resolution of 2 nm. The sample cell was a quartz cuvette (1 cm by 1 cm). The concentration of the prepared catalysts was 1 g/L in the aqueous solution, and the suspension was dispersed using a bath sonicator (100 W) for 10 min.

Light Source Description and Characterization

A xenon arc lamp (1000 W) was selected as a light source in the present Examples. A long-pass optical filter with a cut-off wavelength of 400 nm was used to simulate visible light irradiation at earth's surface. Spectral irradiance, photon fluence, and optical powder density of the xenon lamp were recorded by a spectroradiometer (AvaSpec ULS2048L). The spectral irradiance of the xenon lamp (λ>400 nm) was plotted in FIG. 5, and the photon fluence and the optical powder density were 601 (μmol of photons)/m² s and 16.7 mW/cm², respectively. Applicant notes that g-C₃N₄ with a band gap of 2.72 eV only absorbs photons with a wavelength up to about 460 nm.

Photocatalytic Activity Testing in a Phosphate Buffer

First, 15 mg of g-C₃N₄ was mixed with ultrapure water and dispersed via sonication (Elamsonic P, 37 kHz, 100 W) for 15 minutes. The dispersed g-C₃N₄ suspension and a probe pollutant (i.e., phenol, atrazine, carbamazepine, or sulfamethoxazole) were added to a phosphate buffer solution in a jacketed reactor, giving a total reaction volume of 15 mL, the g-C₃N₄ loading of 1 g/L, the phosphate buffer concentration of 1 mM (pH 7.3), and the pollutant concentration of 100 μM. The reactor had a diameter of 4 cm and starting depth of suspension of 1.5 cm. The surface of the suspension was centered 20 cm below the xenon lamp, which had a beam width of 6 cm. The reaction temperature was maintained at 25° C. The suspension was stirred for 20 minutes in the dark in order to ensure suspension homogeneity, and a sample of 300 μL was next taken to quantify the initial pollutant concentration. Pollutant adsorption onto g-C₃N₄ was negligible, based on the comparison of the measured initial concentration with the concentration in control reactors in absence of g-C₃N₄. The reactor was then irradiated under the xenon lamp (λ>400 nm, typically for 60 minutes), during which aqueous aliquots were withdrawn periodically. The aliquots were next centrifuged at 13,000 rpm for 1 hour in the dark to allow the particles to settle. The supernatant was transferred to a 1.5 mL amber autosampler vial for subsequent analysis via HPLC with photodiode array detection (Shimadzu LC-20AT Prominence HPLC-DAD). For atrazine degradation over multiple photocatalytic cycles, g-C₃N₄ was harvested by centrifugation after each cycle, rinsed with ultrapure water, and reused for the next run. The photocatalyst used after four cycles was characterized by SEM-EDS and ATR-FTIR.

Photocatalytic Activity Testing in a Phosphate Buffer

To explore the influence of water chemistries on photocatalytic performance, particularly water matrices representative of water treatment systems, the reactivity of MCB_(0.07) for atrazine degradation was explored in simulated water samples (1 mM phosphate buffer solution with the presence of 5 mM NaHCO₃, 50 mM CaCl₂, 50 mM MgCl₂, 5 mg/L humic acid sodium salt, 5 mg/L NaNO₃ as N, or 0.1 mM NaHS; pH 7.3 for all solutions except for NaHCO₃ solution with pH 7.5). Ca²⁺ and Mg²⁺ were selected to represent the hardness species in water, NO₃ ⁻, humic acid, and HS⁻ were selected as representative scavengers for oxidative species generated from photocatalytic reactions, and HCO₃ ⁻ was selected to represent alkalinity species that could also react with the oxidative species. Atrazine degradation was also conducted in real water samples collected from a water treatment plant (hereinafter “GWP”) and a wastewater reclamation facility (hereinafter “BRWRF”). Samples were collected from the raw water of GWP (GWP-1), the final effluent from GWP (GWP-4), the effluent after membrane bioreactor treatment in BRWRF (BRWRF-1), and the final effluent from BRWRF (BRWRF-3), and filtered through a 0.45 μm polyvinylidene fluoride (PVDF) membrane before photocatalytic reactions. For the exploration of long-term effect of complex water matrices for photocatalytic activity, MCB_(0.07) was also added to the water samples and magnetically stirred in the dark for 24 hours to pre-foul the photocatalyst before the photocatalytic reactions. Atrazine was added to the reactor 20 minutes before irradiation to ensure suspension homogeneity, and again, there was no evidence of adsorption in any system. pH and alkalinity of these real water samples are listed in Table 1.

TABLE 1 GWP-1 GWP-4 BRWRF-1 BRWRF-3 pH 6.7 7.2 7.5 7.0 Alkalinity 56 61 87 N/A (mg/L as CaCO₃)

HPLC Analysis

The Shimadzu LC-20AT Prominence HPLC System was equipped with a Shimadzu C18 column (4.6×50 mm, 1.8 μm particle size).

The HPLC analysis method for phenol was based on previous work (Arana, J., et al.; Photocatalytic degradation of phenolic compounds with new TiO₂ catalysts. Appl. Catal., B 2010, 100 (1-2), 346-354) and employed a mobile phase of 1 mM sodium acetate: ACN (65:35) at pH 3, a flow rate of 0.75 mL/min, an injection volume of 20 μL, and a 254 nm detection wavelength.

The HPLC analysis method for atrazine was based on previous work (Newcombe, D. A., et al.; Bioremediation of atrazine-contaminated soil by repeated applications of atrazine-degrading bacteria. Appl. Microbiol. Biotechnol. 1999, 51 (6), 877-882) and employed a mobile phase of ultrapure water: ACN (50:50), a flow rate of 1 mL/min, an injection volume of 100 μL, and a 223 nm detection wavelength.

The HPLC analysis method for carbamazepine was based on previous work (Borisover, M., et al.; Enhancement effect of water associated with natural organic matter (NOM) on organic compound-NOM interactions: A case study with carbamazepine. Chemosphere 2011, 82 (10), 1454-1460) and had a mobile phase of ultrapure water: ACN (55:45), a flow rate of 1 mL/min, an injection volume of 25 μL, and a 213 nm detection wavelength.

The HPLC analysis method for sulfamethoxazole was based on previous work (Nalbandian, M. J., et al.; Tailored synthesis of photoactive TiO2 nanofibers and Au/TiO2 nanofiber composites: Structure and reactivity optimization for water treatment applications. Environ. Sci. Technol. 2015, 49 (3), 1654-1663) and had a mobile phase of 5 mM potassium phosphate monobasic (pH adjusted to 5.0): methanol (70:30), a flow rate of 1 mL/min, an injection volume of 20 μL, and a 268 nm detection wavelength.

II. Results and Discussion DFT Simulations

Preliminary DFT studies were performed on an undoped, HSE06-optimized (3×3) g-C₃N₄ supercell (FIG. 6), revealing a planar geometry and a bandgap of 2.75 eV (Table 2, below). The conduction and valence band edges (−1.03 and 1.71 eV), measured with respect to the absolute potential of the standard hydrogen electrode (SHE; 4.44 eV), likewise lie near known experimentally determined values of −0.83 and 1.83 eV. Due to the accuracy of DFT simulations, carbon and phosphorus doping at three inequivalent nitrogen sites (N₁, N₂, and N₃), phosphorus substitution at inequivalent carbon atoms (C₁ and C₂), and the incorporation of phosphorus within the g-C₃N₄ pore (i.e., interstitial doping), all with one dopant introduced to one doping site of HSE06-optimized (3×3) g-C₃N₄ supercell were explored. The doped materials are labeled as A→B doped g-C₃N₄ for further discussion (A is the doping site of N₁, N₂, N₃, C₁, C₂, and Pore, and B is the doping element of C or P). The N₁, N₂, N₃, C₁, C₂, and Pore doping sites are illustrated in FIG. 7.

To determine the thermodynamic ability of these materials to generate ROS (e.g., .OH, O₂ ⁻/HO₂., H₂O₂, and ¹O₂) and holes, their valence band maximum (VBM) and conduction band minimum (CBM) was quantified in conduction with an implicit solvation model, represented by the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energies, respectively. Table 2 provides calculated values of the band gap, the CBM and the VBM of g-C₃N₄ doped with carbon or phosphorus at various locations, in conformity with the description of FIG. 6, based on DFT simulations. The CBM and VBM values are versus a standard hydrogen electrode (SHE). Reported redox potentials for O₂/O₂ ⁻., H₂O₂/.OH, O₂/H₂O₂, O₂ ⁻./H₂O₂, and .OH/H₂O are −0.16, 0.32, 0.70, 0.94 and 2.33 V vs. SHE, respectively. According to the DFT simulations, N₁→C, N₃→C, N₁→P, N₂→P, and N₃→P doped g-C₃N₄ can produce O₂ ⁻. via one-electron reduction of O₂ because their CBM is more negative than the redox potential of O₂/O₂ ⁻. (E₀(O₂/O₂ ⁻.)=−0.16 V vs SHE). All doped materials are able to produce H₂O₂ and —OH from the one-electron reduction of O₂ ⁻. and H₂O₂, respectively (E₀(O₂ ⁻./H₂O₂)=0.94 V and E₀(H₂O₂/.OH)=0.32 V vs SHE). However, O₂ reduction for O₂ ⁻. formation is the first step for ROS production on the conduction band (i.e., sequential reduction of O₂→O₂ ⁻.→H₂O₂→.OH), and those doped g-C₃N₄ that cannot reduce O₂ may not produce sufficient ROS and thus result in low photocatalytic activity for contaminant degradation. Multielectron reduction could facilitate ROS production on the conduction band because it is more thermodynamically favorable than one-electron reduction (E₀(O₂/H₂O₂)=0.70 V vs SHE), but the loading of co-catalysts (e.g., Pt, Au, and Cu(II)) may be required.

TABLE 2 Composition (Doping site) Band Gap (eV) CBM (V) VBM (V) Undoped g-C₃N₄ 2.75 −1.03 1.71 N₁ → C doped g-C₃N₄ 2.58 −1.01 1.57 N₂ → C doped g-C₃N₄ 2.08 0.05 2.13 N₃ → C doped g-C₃N₄ 2.94 −0.67 2.28 N₁ → P doped g-C₃N₄ 2.06 −0.71 1.36 N₂ → P doped g-C₃N₄ 1.69 −0.20 1.49 N₃ → P doped g-C₃N₄ 2.90 −0.70 2.20 C₁ → P doped g-C₃N₄ 1.93 0.12 2.05 C₂ → P doped g-C₃N₄ 1.86 0.19 2.05 Pore → P doped g-C₃N₄ 1.14 −0.06 1.08

FIG. 8 is an illustration of the optimized geometry of undoped and doped forms of g-C₃N₄. As illustrated, both N₁→C and N₃→C doped g-C₃N₄ exhibit a planar geometry similar to that of undoped g-C₃N₄. Conversely, N₂→C doped g-C₃N₄ is characterized by a significant out-of-plane deformation. The N₁₋₃→P geometries are collectively more distorted, each exhibiting some degree of undulation due to the bulky phosphorus substituent, and are presumably less thermodynamically stable than their carbon-doped counterparts due to strain. Following these observations, the hole distribution in the valence band (HOMO) and electron distribution of the conduction band (LUMO) of these materials were determined. While the HOMO of undoped g-C₃N₄ is relatively delocalized, the LUMO exhibits a staggered distribution on alternating trimers. The same trend is observed for the LUMO of carbon-doped systems, though N₂→C doped g-C₃N₄ exhibits a higher degree of localization due to a pronounced “tenting” of the g-C₃N₄ sheet. The HOMO of carbon-doped g-C₃N₄ is markedly different from the undoped material and is distributed around the dopant site. While the orbital structure will undergo remodeling subsequent to exciton formation and charge migration, it is reasonable to speculate that the impurity-localized valence electrons provide the primary sites for localized hole formation within the valence band of doped g-C₃N₄.

Photocatalytic Performance of C- and P-Doped g-C₃N₄

The effect of nonmetal doping on the photocatalytic performance of g-C₃N₄ was evaluated by testing MCB_(x) or MCE_(y) for phenol and/or atrazine degradation under simulated visible sunlight irradiation (λ>400 nm, xenon lamp) and comparing the activity with MC.

FIG. 9 is a graphical representation of the photocatalytic activity for phenol degradation of MCB_(x) compositions synthesized with varying amounts of barbituric acid. As shown in FIG. 10, the synthesized MCB_(x) exhibited significantly enhanced photocatalytic activity, especially at the low barbituric acid content (i.e., x=0.01-0.07). MCB_(0.07) had the highest reaction rate constant, and its reactivity was enhanced by 2.8-fold compared to that of MC (0.8±0.08 vs 0.3±0.02 m²/(mol of photons). The photocatalytic activity of MCB_(x) significantly decreased at higher barbituric acid mass loadings (x>0.1), likely due to excessive carbon doping promoting charge recombination.

FIG. 10 is a graphical representation of the photocatalytic activity for phenol degradation of MCE_(y) compositions synthesized with varying amounts of etidronic acid. As can be seen, only MCE_(0.03) and MCE_(0.05) performed marginally better than the undoped MC composition.

FIG. 11 is a graphical representation of the photocatalytic activity for atrazine degradation of MCE_(y) compositions synthesized with varying amounts of etidronic acid. As can be seen, reactivity increase was observed for atrazine degradation on MCE_(0.01) that had the lowest phosphorus doping level 0.6±0.1 and 0.3±0.02 m²/(mol of photons) for MCE_(0.01) and MC, respectively). A slight activity increase was also observed for MCE_(0.03) as compared to MC.

The experimental results are in agreement with DFT simulation results with carbon-doped g-C₃N₄ showing an enhanced activity compared to that of phosphorus-doped g-C₃N₄. The carbon-doped supramolecule-based g-C₃N₄ with an optimum photocatalytic activity (MCB_(0.07)), undoped supramolecule-based g-C₃N₄ (MC), and conventional g-C₃N₄ (U and M) were selected for further material characterization and water treatment applications.

Relationship Between Photocatalytic Activity and g-C₃N₄ Properties.

FIG. 12 shows photocatalytic degradation kinetics of phenol and persistent organic micropollutants on g-C₃N₄ compositions in the phosphate buffer under simulated visible sunlight irradiation (λ>400 nm, xenon lamp). MCB_(0.07) showed the highest photocatalytic activity for atrazine, sulfamethoxazole, and carbamazepine compared to that of other g-C₃N₄ samples, and its reactivity was on par with U for phenol degradation. M had the lowest reactivity compared to that of its counterpart g-C₃N₄ samples. Of the four probe contaminants, atrazine is the most photocatalytically degradable on g-C₃N₄ samples (except for U), and carbamazepine is the most persistent in photocatalytic reactions.

Atrazine degradation was also explored on MCB_(0.07) over four repeated cycles, and no reactivity loss or morphological/chemical property change of the photocatalyst was observed. For each of the four cycles, an MCB_(0.07) loading of 1 g/L, an initial atrazine concentration of 100 μm, a 1 mM phosphate buffer (pH 7.3), and xenon lamp irradiation at λ>400 nm was used. FIG. 13 is a graphical display of photocatalytic rate constants of atrazine degradation on MCB_(0.07) under visible light irradiation over the four cycles (error bars represent 95% confidence intervals. FIG. 14 is an ATR-FTIR spectra comparing fresh MCB_(0.07) and MCB_(0.07) recovered after atrazine degradation. FIG. 15 shows SEM images of fresh MCB_(0.07) (left) and MCB_(0.07) recovered after atrazine degradation (right).

The measured photocatalytic activity for contaminant degradation could be influenced by mass transfer and contaminant adsorption on g-C₃N₄. Nonetheless, as will be discussed below, mass transfer limitation was eliminated in the reaction, and no contaminant adsorption was measured in the dark experiments. In addition, all g-C₃N₄ samples showed a similar negative ζ-potential (i.e., −28.5 to −37.8 mV at pH 7.3), and they were not expected to interact strongly with neutral contaminants in the reaction solution at pH 7.3 (pKa's of phenol, atrazine, sulfamethoxazole, and carbamazepine are 10.0, 1.7, 1.4/5.8, 2.3/13.9, respectively).

The enhancement of photocatalytic activity could be determined by the following key photocatalyst properties: (i) an increased surface area, (ii) improved light harvesting, and (iii) promoted charge separation. Photocatalysis is a surface-mediated reaction, and the increased surface area provides more active sites for the contaminants to reside and react. The improvement of light harvesting and charge separation enables the generation of more electrons and holes for photocatalytic reactions. MCB_(0.07) exhibited the highest surface area, and its reactivity outperformed M and MC for the degradation of all probe contaminants. The charge separation of MCB_(0.07) and MC was significantly promoted compared to M, and M showed the lowest reactivity for contaminant degradation. The low carbon doping of MCB_(0.07) did not change its band gap, but midgap states possibly increased visible light absorption and photocatalytic activity. The results indicate that the enhanced surface area, visible light absorption, and charge separation of MCB_(0.07) synergistically contribute to improving the photocatalytic activity.

Selective Contaminant Degradation on g-C₃N₄.

It is worth noting that g-C₃N₄ is selective for contaminant degradation. MCB_(0.07) is 1.8 times more reactive for the degradation of atrazine than phenol; however, U is 3.9 times more reactive for the degradation of phenol than atrazine. Similar selective degradation of sulfamethoxazole was also observed in comparison with phenol or atrazine. To understand the mechanism of selective contaminant removal, the significance of the ROS and hole for the photocatalytic degradation of phenol and atrazine was explored. Scavenger tests were conducted to quench the reactions between contaminants and a specific oxidative species, and the inhibition of reactivity was used to evaluate the contribution of the specific oxidative species to photocatalytic degradation. The results, as shown in FIG. 16, indicated that the addition of tert-butyl alcohol (10 mM), a .OH scavenger, reduced the reactivity for phenol degradation by 60% on U compared to 33% on MCB_(0.07). The .OH scavenger test also showed 55% of reactivity inhibition for atrazine degradation on U, in contrast to no inhibition for atrazine degradation on MCB_(0.07). However, the addition of ammonium oxalate (10 mM), a hole scavenger, significantly inhibited the reactivity for phenol and atrazine degradation on both U and MCB_(0.07) from 74 to 86%. The addition of L-histidine (10 mM), a ¹O₂ scavenger, reduced the reactivity of phenol degradation by 76% on U compared to 55% on MCB_(0.07) and fully inhibited the reactivity for atrazine degradation on both U and MCB_(0.07). For these experiments, a photocatalyst (U or MCB_(0.07)) loading of 1 g/L, an initial atrazine concentration of 100 μm, a 1 mM phosphate buffer (pH 7.3), and xenon lamp irradiation at λ>400 nm was used.

With being bound to any particular theory, it is believed that the production of oxidative species on g-C₃N₄ is structurally sensitive; different g-C₃N₄ compositions generate different types and amounts of oxidative species. Phenol is known to be more reactive with .OH than atrazine with .OH, and the second-order rate constant of .OH-phenol is 5.9-fold higher than that of .OH-atrazine (1.4×10¹⁰ vs 2.4×10⁹ s⁻¹ M⁻¹). U may generate more .OH than MCB_(0.07), and quenching .OH had more pronounced inhibition for phenol degradation. MCB_(0.07) may produce a significant amount of other ROS, e.g., O₂ ⁻./HO₂. and ¹O₂, to facilitate atrazine degradation. Though .OH is generally more reactive (second-order reaction rate constant between ROS and organics are 10⁶-10¹⁰, 10³-10¹⁰, or <10⁸ M⁻¹ s⁻¹ for .OH, ¹O₂, or O₂ ⁻./HO₂., respectively), its steady-state concentration is orders of magnitude lower in water compared to that of other ROS. The other ROS, especially ¹O₂, may be a leading contributor to atrazine degradation; quenching .OH had a negligible effect on atrazine degradation on MCB_(0.07), but quenching ¹O₂ completely deactivated photocatalytic atrazine degradation. In contrast, U could produce .OH as one dominant ROS, and hence atrazine degradation on U is slower, and quenching .OH reduces the reactivity significantly. The hole and ¹O₂ are the most dominant oxidative species for contaminant degradation, regardless of g-C₃N₄ properties. O₂ ⁻. and H₂O₂ were also identified in the photocatalytic degradation of phenol on U, and their contribution to reaction kinetics was also critical (FIG. 17). In FIG. 17, the reactivity inhibition (%) was calculated by dividing the reactivity difference without and with the scavenger by the reactivity without the scavenger. For these experiments, a photocatalyst (U or MCB_(0.07)) loading of 1 g/L, an initial atrazine concentration of 100 μm, a 1 mM phosphate buffer (pH 7.3), and Xenon lamp irradiation at λ>400 nm was used.

Performance Comparison in Matrixes Representative of Water and Wastewater Treatment.

For all experiments conducted in the simulated and real water samples and with both fresh and aged MCB_(0.07), little to no inhibition was observed in atrazine degradation, as shown in FIG. 18. Graphical display (a) of FIG. 18 shows atrazine degradation by a freshly prepared MCB_(0.07) suspension in simulated water samples. Graphical display (b) of FIG. 18 shows atrazine degradation by a 24-hour aged MCB_(0.07) suspension in simulated water samples. Graphical display (c) of FIG. 18 shows atrazine degradation by a freshly prepared MCB_(0.07) suspension in real water samples. Graphical display (d) of FIG. 18 shows atrazine degradation by a 24-hour aged MCB_(0.07) suspension in real water samples. In the experiments, simulated visible sunlight irradiation (xenon lamp, λ>400 nm) was used. The initial concentration of atrazine was 100 μM in simulated water samples and 20 μM in real water samples. Atrazine degradation was faster with the lower initial concentration of 20 μM. Control experiments were conducted under the same experimental conditions in a phosphate buffer (pH 7.3, 1 mM) prepared from ultrapure water. The foulants or natural water constituents were amended into the phosphate buffer for simulated water tests. No phosphate buffer was used for the real water tests. Photocatalyst loading was 1 g/L. The excellent photocatalytic performance of g-C₃N₄ in complex water matrixes may be attributed to the large surface area, high porosity, the polymeric nature of the material without metal loading, and the selective ROS production.

Increased surface area and porosity may afford sufficient sites to interact with contaminants even when foulants or natural water constituents are at a high concentration (i.e., mM of foulants or constituents vs μM of contaminants). Noble metals used in photocatalysis (e.g., Au) are reactive and susceptible to fouling, and the polymeric nature of g-C₃N₄ with the presence of only carbon and nitrogen mitigates the likelihood of photocatalyst deactivation. In addition, the hydrophilic nature of g-C₃N₄ reduces the adsorption of organic or biological foulants, and the tri-s-triazine unit in g-C₃N₄ is not expected to bind strongly to the carboxylate group of NOM, in contrast to TiO₂.

The selective production of ROS may also contribute to the minimal inhibition of photocatalytic activity in complex water matrices. —OH is the most powerful, nonselective radical generated in most AOPs and is attractive for environmental applications because it can degrade most organic contaminants at near diffusion-limited rates. However, the nonselective destruction of contaminants can be easily compromised when non-target chemicals are present, including NOM and other background constituents present in raw natural water or (partially) treated water and wastewater. In the presently described system, MCB_(0.07) may generate other ROS predominantly rather than .OH, such as ¹O₂ and O₂ ⁻./HO₂., which are more selective for contaminant degradation. For example, ¹O₂ selectively oxidizes electron-rich moieties of contaminants with the presence of NOM, and O₂ ⁻./HO₂. facilitates the degradation of halogenated compounds because of the synergy of reductive dehalogenation and the oxidation of carbon backbones (O₂ ⁻./HO₂. can act as both a reductant and an oxidant).

The exploration of the structural sensitivity is significant for the application of g-C₃N₄ in contaminant degradation because the synthesis and properties of g-C₃N₄ compositions can be tailored to selectively degrade a certain group of highly toxic, low concentration contaminants with minimized inhibition from co-contaminants, natural water constituents, or foulants. It may also be useful for designing photocatalysts for selective oxidation and conversion of contaminants to value-added products (e.g., benzene oxidation to phenol). Further studies may be helpful to quantitatively analyze the production of oxidative species and identify key g-C₃N₄ properties for the selective generation of oxidative species and degradation of contaminants. Factors beyond the generation of oxidative species, such as the affinity of g-C₃N₄ to contaminants, may also be important for the selectivity in contaminant degradation. The affinity between the photocatalyst and contaminant may be tailored for selective reactions.

Influence of Mass Transfer Processes on Observed Reaction Rates

The following calculations were performed to investigate the potential effects of aqueous/solid and intraparticle mass transfer processes on the observed reaction rates. The results indicate that mass transfer was not expected to limit the observed reaction rates in the presently disclosed systems.

Aqueous/Solid Mass Transfer Limitations

Here, the lower limit for the aqueous/solid mass transfer rate constant for atrazine degradation on MCB_(0.07) (k_(aq/s)a) was estimated and compared to the measured reaction rate constant. Atrazine degradation on MCB_(0.07) was selected because it showed the fastest degradation kinetics compared to the other photocatalytic reactions of the present application. Criteria for the evaluation of potential influence of aqueous/solid mass transfer limitations on the observed rate constants are 1) No aqueous/solid mass transfer limitations expected if calculated k_(aq/s)a is much greater than the largest measured k_(obs, MCB) value; and 2) Significant potential for aqueous/solid mass transfer limitations is expected if k_(aq/s)a is close to or less than the measured k_(obs, MCB) value.

The slip velocity method is used to calculate the mass transfer coefficient (k_(aq/s)) for particles traveling at the slip velocity (u_(t)) relative to the suspending liquid. Because the particle size of MCB_(0.07) was much smaller than 1 mm, Stokes' law is assumed to be applicable and the particle's slip velocity is calculated by:

$\begin{matrix} {u_{t} = \frac{{gd}_{p}^{2}\left( {\rho_{p} - \rho} \right)}{18\mu}} & (3) \end{matrix}$

where g is the gravity constant, d_(p) and ρ_(p) are the hydrodynamic diameter and density of the photocatalyst particle, respectively, ρ is the density of water, and μ is the absolute viscosity of water.

The aqueous/solid mass transfer coefficient is then estimated by the following expression:

$\begin{matrix} {k_{{aq}/s} = {{\frac{D_{mol}}{d_{p}}{Sh}} = {\frac{D_{mol}}{d_{p}}\left( {2 + {0.6\; {Re}^{0.5}{Sc}^{0.33}}} \right)}}} & (4) \end{matrix}$

where D_(mol) is the molecular diffusion coefficient of the reacting solute (atrazine), Sh is the Sherwood number, Re is the modified Reynold's number, and Sc is the Schmitt number. The last two parameters are calculated by the following expressions:

$\begin{matrix} {{Re} = \frac{d_{p}u_{t}}{v_{H_{2}O}}} & (5) \\ {{Sc} = \frac{v_{H_{2}O}}{D_{mol}}} & (6) \end{matrix}$

where ν_(H2O) is the kinematic viscosity of water. The molecular diffusion coefficient for atrazine in water is calculated using:

$\begin{matrix} {D_{mol} = \frac{13.26 \times 10^{- 5}}{{\mu^{1.14}(v)}^{0.589}}} & (7) \end{matrix}$

where D_(mol) is in the unit of cm²/s, μ is in the unit of g m⁻¹ s⁻¹, and v′ is the molar volume of atrazine, which is 250.6 cm³/mol, calculated using the LeBas method. Plugging the results into equation 5, using μ=1.002 g/(m s) (at 20° C.), then D_(mol)=5.11×10⁻¹⁰ m²/s. The values and other physical constants summarized in Table 3 are then used in equations 3-6 to determine that k_(aq/s)=4.30×10⁻⁴ m/s.

TABLE 3 Constant Value D_(mol) of atrazine 5.11 × 10⁻¹⁰ m²/s Gravity constant, g 9.81 m/s² Photocatalyst particle 2.39 × 10⁻⁶ m, determined diameter, d_(p) by dynamic light scattering Kinematic viscosity 1.003 × 10⁻⁶ m²/s (at 20° C.) of water, ν_(H2O) Particle Density, ρ_(p) 1.34 × 10⁶ g/m³ Water density, ρ 9.98 × 10⁵ g/m³ (at 20° C.) Absolute viscosity of water, μ 1.002 g/(m s) (at 20° C.)

To calculate the mass transfer rate constant, the mass transfer coefficient should be multiplied by the geometric surface area of the catalyst per volume of solution, a:

$\begin{matrix} {a = {\frac{{total}\mspace{14mu} {surface}\mspace{14mu} {area}}{{total}\mspace{14mu} {volume}} = {\frac{{SA}_{p} \times M}{\rho_{p} \times V_{p}} \times \frac{1}{V_{R}}}}} & (8) \end{matrix}$

where SA_(p) is the geometric surface area of one MCB_(0.07) aggregate, which is assumed to have a spherical structure; Mis the mass of photocatalyst in the reactor; V_(p) is the volume of one MCB_(0.07) aggregate; and VR is the volume of reaction suspension. For the fastest reaction measured, M=0.015 g and VR=0.015 L, so a=1871 m⁻¹ and k_(aq/s)a=0.8 s⁻¹. This value is about 3 orders-of-magnitude larger than the measured k_(obs,MCB) value (8.0×10⁻⁴ s⁻¹). Thus the results indicate the aqueous/solid mass transfer is expected to have negligible limitation on the measured reaction rates.

Intraparticle Mass Transfer Limitations

The potential of intraparticle mass transfer resistance is also investigate by using the following criteria: 1) no resistance to pore diffusion if (k_(obs)L²)/D_(e)<1, and 2) significant resistance to pore diffusion if (k_(obs)L²)/D_(e)>1, where L is characteristic diffusion path length for the photocatalyst and D_(e) is the effective diffusivity of the reacting solute. L and D_(e) are estimated using the following equations:

$\begin{matrix} {L = {\frac{1}{6}d_{p}}} & (9) \\ {D_{e} = \frac{D_{mol}\theta}{\tau}} & (10) \end{matrix}$

where θ is the porosity of the photocatalyst particle (typically ranging from 0.2-0.7) and τ is the tortuosity factor (typically ranging from 2-10). The most conservative values from each range are used to maximize the possibility that the criterion (k_(obs)L²)/D_(e)>1 is met (i.e., we chose the smallest θ (0.2) and largest τ (10) in order to obtain the smallest possible D_(e) value), and, in turn, the largest possible value for equation 9 is L=3.99×10⁻⁷ m and the largest possible value for equation 10 is D_(e)=1.02×10⁻¹¹ m₂/s.

The largest observed reaction rate constant was 8.0×10's⁻¹ for atrazine degradation on MCB_(0.07). This rate constant and the values of L and D_(e) calculated above are then used to test the two criteria outlined above to find a (k_(obs)L²)/D_(e) value of 1.25×10⁻⁵ (<<1). Because the (k_(obs)L²)/D_(e) value is several orders-of-magnitude less than one, intraparticle mass transfer resistance is negligible on the time scale over which the photocatalytic degradation was observed the presently described system.

Photocatalytic Performance of MCB_(0.07) g-C₃N₄ in Antimicrobial Applications

Disinfection Experiments of Planktonic E. coli.

To generate a standard curve, E. coli was cultured in Luria-Bertani broth (LB) at 37° C. with mixing (120 rpm) and was harvested during its late-exponential phase by centrifugation. The E. coli was then resuspended with phosphate-buffered saline (PBS) and then the suspension was centrifuged. The supernatant was discarded. This process was repeated for three time. After being washed with PBS, the E. coli was resuspended in PBS to form a stock bacterial suspension. Next, the stock suspension was diluted with PBS to form a series of concentrations (10%, 20%, . . . , 100% of the original concentration). The OD₆₀₀ values of bacterial solutions with different concentrations were measured respectively. Five concentrations were selected to conduct plate counting. Bacterial solutions were diluted in series. The relationship between solution concentration and colony-forming units (CFU) were recorded.

To test the antimicrobial activity of g-C₃N₄, 25 ml of a bacterial suspension (E. coli in PBS, 1×10⁷ CFU/mL) was mixed with 0.001 g of MCB_(0.07) g-C₃N₄ powder in a sterile glass beaker. The beaker was placed under a white light emitting diode (LED) lamp (7 W) for bacterial inactivation. The distance between the surface of the bacterial suspension and the LED lamp was maintained at 15 cm. Bacterial suspension samples were withdrawn from the beaker with pipette every half an hour. The samples were duplicated, diluted in series with the PBS buffer, and plate counting was conducted to determine bacterial viability (FIG. 19). As can be seen in FIG. B, after two hours, the number of culturable E. coli decreased from 1×10⁷ to about 4×10⁴ CFU/mL, equating to a 99.6% reduction.

Biofilm Development Experiments.

S. epidermidis was cultured in tryptic soy broth (TSB) at 37° C. with mixing (120 rpm). S. epidermidis was harvested during its late-exponential phase by centrifugation and diluted in the PBS buffer to prepare a bacterial suspension (OD₆₀₀=0.5). MCB_(0.07) g-C₃N₄ powder was then hydraulically pressed to form thin coupons. The MCB_(0.07) g-C₃N₄ coupons were placed into a sterile six-well plate, and completely submerged by the bacterial suspension (2 ml for each coupon in each well) to form a system. The system was first incubated at 37° C. for 24 h without light and mixing to ensure effective bacterial attachment on the MCB_(0.07) g-C₃N₄ coupon surface. Then, the suspension was evacuated by aspiration, and the coupons were gently rinsed with PBS three times to remove loosely attached cells. Next, the coupons were transferred to a new sterile six-well plate, and 2 ml of 10-fold diluted TSB was added to submerge the coupons. The system was incubated at 37° C. with a mixing rate of 80 rpm under LED irradiation and in the dark (control experiment). TSB was replenished every 24 hours for the system and the system was incubated for 3 days. At the end of the experiments, the MCB_(0.07) g-C₃N₄ coupons were taken out and gently rinsed with the PBS buffer three times. The Filmtracer LIVE/DEAD Biofilm Viability Kit was used to stain the biofilms on the coupons, and a confocal microscope was utilized to image the biofilms. The confocal microscopy results are shown in FIG. 20. A thick biofilm with a majority of live cells was developed on the g-C₃N₄ coupon in the dark, however, negligible bacteria survived on the g-C₃N₄ under LED irradiation.

Optical Coherence Tomography (OCT) Analysis.

S. epidermidis was cultured in tryptic soy broth (TSB) at 37° C. with mixing (120 rpm). S. epidermidis was then harvested during its late-exponential phase by centrifugation and diluted in the PBS buffer to prepare a bacterial suspension (OD₆₀₀=0.5). MCB_(0.07) g-C₃N₄ powder was then hydraulically pressed to form thin coupons. The MCB_(0.07) g-C₃N₄ coupons were placed into a sterile six-well plate, and completely submerged by the bacterial suspension (2 ml for each coupon in each well) to form a system. The system was first incubated at 37° C. for 24 h without light and mixing to ensure effective bacterial attachment on coupon surface. Then, the suspension was evacuated by aspiration, and the coupons were gently rinsed with PBS three times to remove loosely attached cells. Next, the coupons were transferred to a new sterile six-well plate, and 2 ml of 10-fold diluted TSB was added to submerge the coupons. The system was incubated at 37° C. with a mixing rate of 80 rpm under LED irradiation and in the dark (control experiment). TSB was replenished every 24 hours for the system and the system was incubated for 2 days. The coupons were analyzed by optical coherence tomography (OCT) in the six-well plates directly. FIG. 21 shows OCT images of biofilms developed on the surface of MCB_(0.07) g-C₃N₄ coupons in the dark (left) and under visible light (right). A biofilm with a thickness of 50-100 μm were developed on the g-C₃N₄ coupon in the dark, however, no biofilm was observed on the MCB_(0.07) g-C₃N₄ under LED irradiation.

Characterization of g-C₃N₄ Compositions

FIG. 22 is a graphical representation of the XRD patterns of g-C₃N₄ compositions formed from urea (U), melamine (M), melamine and cyanuric acid (MC), and melamine, cyanuric acid, and barbituric acid (MCB_(0.07)), respectively. As can be seen, all g-C₃N₄ samples had a similar XRD pattern that could be ascribed to a typical graphite-like structure and the introduction of cyanuric acid and/or barbituric acid may promote polymer-like growth and more defects in g-C₃N₄. Specifically, the peak 13° corresponding to in-plane ordering of tri-s-triazine units is less pronounced for supramolecule-based g-C₃N₄ (that is, MC and MCB_(0.07)) than M, indicating that more defects may be generated in the growth of g-C₃N₄ with the addition of cyanuric acid and/or barbituric acid. The other peak around 27.6°, representative of (002) interlayer stacking, became broader for supramolecule-based g-C₃N₄ and U, suggesting their crystallinities are lower than that of M. The results may indicate that polymer-like growth was dominated in U, MC, and MCB_(0.07) compared to the growth of a graphitic structure in M.

ATR-FTIR analysis of each photocatalyst (FIG. 23) showed absorption bands characteristic of g-C₃N₄: six bands in the 1200-1650 cm⁻¹ region for stretching modes of C—N heterocycles and one band at 805 cm⁻¹ for triazine.

FIG. 24 is an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from urea (U). FIG. 26 further provides a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of the U composition. The g-C₃N₄ composition formed from urea has a porous structure, possibly due to a large amount of gas production in the thermal polycondensation of urea (e.g., NH₃ and H₂O).

FIG. 25 is an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from melamine (M). FIG. 27 further provides a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of the M composition. A typical condensed, layered structure of the g-C₃N₄ composition formed from melamine was observed with the presence of fewer pores than when formed from urea, likely due to a lesser extent of structural reorganization and reduced gas emission.

FIG. 26 is an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from melamine and cyanuric acid (MC). FIG. 28 further provides a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of the MC composition. The addition of cyanuric acid created a loose, porous structure, as expected from the self-templating of cyanuric acid with limited thermal stability.

FIG. 27 is an SEM image and a TEM image (inset) of a g-C₃N₄ composition formed from melamine, cyanuric acid and barbituric acid (MCB_(0.07)). FIG. 29 further provides a table (inset) providing the surface area, pore volume, and bulk carbon to nitrogen (C/N) mass ratio of the MCB_(0.07) composition. The addition of cyanuric acid created a loose, porous structure, as expected from the self-templating of cyanuric acid with limited thermal stability. Further introduction of barbituric acid for MCB_(0.07) synthesis did not lead to any notable change in the sample morphology, possibly because of the low loading of barbituric acid (i.e., 0.07 g).

The surface area and porosity of g-C₃N₄ samples were characterized by liquid N₂ adsorption, and the adsorption isotherms and pore size distribution indicated that U, MC, and MCB_(0.07) compositions mainly contained mesopores. The M composition had the lowest BET surface area and pore volume in all g-C₃N₄ samples, as supported by the SEM and TEM results. The BET surface area and pore volume of the MC composition increased by 8.0- and 6.6-fold compared to those of the M composition and were also higher than those of the U composition. The MCB_(0.07) had the highest surface area and pore volume compared to other compositions. Also, the C/N mass ratio increases from 0.59 (U and M compositions) to 0.60 (the MC composition) to 0.61 (the MCB_(0.07) composition).

FIG. 28 shows SEM images of MCB_(0.07) prepared in ethanol (a) and water (b). As shown, preparation in ethanol leads to MCB_(0.07) having a pancake-like structure while preparation in water leads to MCB_(0.07) having an irregular rod-/particle-like structure.

Optical properties of the g-C₃N₄ compositions, including band gap and optical absorption, were characterized to evaluate its capability of harvesting and utilizing visible photons. g-C₃N₄ is an indirect band gap photocatalyst, and all g-C₃N₄ compositions had a similar band gap of 2.72 eV (harvesting photons with λ≦ca. 460 nm, FIG. 29), which is in agreement with the presently disclosed DFT simulation results for undoped g-C₃N₄. The addition of cyanuric acid and barbituric acid did not change the band gap of g-C₃N₄, in contrast to DFT predictions, likely due to the low dopant level (C/N mass ratio of 0.61 vs 0.59). Nevertheless, the MCB_(0.07) composition showed noticeable band-tail absorption in the visible light region (>460 nm) compared to undoped g-C₃N₄ compositions (U, M, and MC in FIG. 29), likely due to the presence of midgap states, i.e., the electronic states located within the band gap. The midgap states can accommodate photoexcited electrons from the valence band, resulting in the absorption of photons with energies smaller than the band gap for photocatalytic reactions. In addition to intrinsic photon absorption as reflected by the band gap, the morphology, structure, and particle size of g-C₃N₄ in reaction suspension can also impact the photon absorption due to light reflection and scattering on materials. The U composition had the highest absorption of visible light (λ>400 nm), followed by the other samples (i.e., M, MC, and MCB_(0.07) compositions) with similar optical absorption, as illustrated in FIG. 30. Increased photon absorption of the U composition may improve the photocatalytic activity for contaminant degradation.

Improved charge separation may enhance the photocatalytic activity of g-C₃N₄ because of an increased amount of charge carriers for photocatalytic reactions. PL intensity, representative of radiative charge recombination, was used as an indirect evidence to characterize charge separation. The PL intensity of U, MC, and MCB_(0.07) was similar and significantly lower than that of M (FIG. 31), and it suggests that charge recombination may be the most pronounced in M, and its photocatalytic performance may be limited. The PL peak of U, MC, and MCB_(0.07) also red-shifted compared to that of M (FIG. 31). The reduction of PL intensity and red-shifted peaks indicate that the addition of cyanuric acid and barbituric acid for the preparation of supramolecule-based g-C₃N₄ may lower the charge recombination compared to M derived from melamine only. Holes are generally less mobile than electrons (i.e., diffusion length of several nanometers vs micrometers), and increased surface area and porosity in U, MC, and MCB_(0.07) could facilitate the migration of holes to the surface and subsequent reactions with contaminants rather than recombination with electrons. Carbon dopants may also facilitate hole localization and improve the reaction between charge carriers and contaminants, as suggested by DFT simulations. Nevertheless, the PL only qualitatively characterizes the extent of radiative charge recombination but not nonradiative charge recombination (dissipation as heat rather than photon emission), and it may not necessarily explain the photocatalytic activity. For example, the PL intensity of U and MC was lower compared to that of MCB_(0.07), which suggested that U and MC might exhibit an increased charge separation. In contrast, the photocatalytic activity of MCB_(0.07) was equal to or higher than that of U and MC for contaminant degradation.

It will be apparent that various other modifications and adaptations of the embodiments or application will be apparent to the person skilled in the art after reading the foregoing disclosure without departing from the scope of the application and it is intended that all such modifications and adaptations come within the scope of the appended claims. 

What is claimed is:
 1. A method of forming a supramolecule-based, carbon-doped graphitic carbon nitride (g-C₃N₄) composition, the method comprising: forming a suspension comprising a solvent and a precursor mixture comprising melamine, cyanuric acid, and barbituric acid; drying the suspension at a first temperature to remove the solvent and form a supramolecular complex; heating the supramolecular complex at a second temperature to form a carbon-doped g-C₃N₄ composition.
 2. The method of claim 1, wherein the precursor mixture comprises about 50 wt % melamine, about 2.5-49.75 wt % cyanuric acid, and about 0.25-47.5 wt % barbituric acid.
 3. The method of claim 1, wherein the precursor mixture comprises about 50 wt % melamine, about 47.5-49.75 wt % cyanuric acid, and about 0.25-2.5 wt % barbituric acid.
 4. The method of claim 1, wherein the second temperature is between about 450° C. and about 600° C.
 5. An article having a surface coated with a carbon-doped g-C₃N₄ composition formed according to claim
 1. 6. The article of claim 5, the article being any one of a kitchen counter-top, a cutting board, a hand-gripping portion of an appliance, a hand-gripping portion of a cabinet, a hand-gripping portion of a drawer, a desk, a table, a light fixture, a light switch, a food package, and a food processing surface.
 7. A water treatment system comprising a carbon-doped g-C₃N₄ composition formed according to claim
 1. 8. The water treatment system of claim 7, wherein the carbon-doped g-C₃N₄ composition photocatalytically degrades persistent organic micropollutants comprising pharmaceuticals and personal care products (PPCPs), endocrine disrupting compounds (EDCs), pesticides, and herbicides in the presence of ultraviolet (UV) or visible light.
 9. A method of forming a supramolecule-based, phosphorus-doped graphitic carbon nitride (g-C₃N₄) composition, the method comprising: forming a suspension comprising a solvent and a precursor mixture comprising melamine, cyanuric acid, and etidronic acid; drying the suspension at a first temperature to remove the solvent and form a supramolecular complex; heating the supramolecular complex at a second temperature to form a phosphorus-doped g-C₃N₄ composition.
 10. The method of claim 9, wherein the precursor mixture comprises about 50 wt % melamine, about 37.5-49.75 wt % cyanuric acid, and about 0.25-12.5 wt % etidronic acid.
 11. The method of claim 9, wherein the precursor mixture comprises about 50 wt % melamine, about 47.5-49.75 wt % cyanuric acid, and about 0.25-2.5 wt % etidronic acid.
 12. The method of claim 9, wherein the second temperature is between about 450° C. and about 600° C.
 13. An article having a surface coated with a phosphorus-doped g-C₃N₄ composition formed according to claim
 9. 14. The article of claim 13, the article being any one of a kitchen counter-top, a cutting board, a hand-gripping portion of an appliance, a hand-gripping portion of a cabinet, a hand-gripping portion of a drawer, a desk, a table, a light fixture, a light switch, a food package, and a food processing surface.
 15. A water treatment system comprising a phosphorus-doped g-C₃N₄ composition formed according to claim
 9. 16. The water treatment system of claim 15, wherein the phosphorus-doped g-C₃N₄ composition photocatalytically degrades persistent organic micropollutants comprising pharmaceuticals and personal care products (PPCPs), endocrine disrupting compounds (EDCs), pesticides, and herbicides in the presence of UV or visible light.
 17. A method of treating a contaminant-containing water source, the method comprising: introducing contaminant-containing water to a doped graphitic carbon nitride (g-C₃N₄) composition comprising any one of a carbon-doped g-C₃N₄ and phosphorus-doped g-C₃N₄; and subjecting the contaminant-containing water and doped g-C₃N₄ composition to a UV light or a visible light.
 18. The method of claim 17, wherein the method is performed at room temperature.
 19. The method of claim 17, further comprising stirring the contaminant-containing water and doped g-C₃N₄ composition.
 20. The method of claim 17, wherein the contaminant is any one of a pharmaceutical and personal care product (PPCP), and endocrine disrupting compound (EDC), a pesticide, and a herbicide.
 21. An article, the article comprising: a surface; and a antimicrobial coating disposed on the surface, the coating including a graphitic carbon nitride (g-C₃N₄) composition comprising: a carbon-doped g-C₃N₄ composition, a phosphorus-doped g-C₃N₄ composition, or a combination thereof.
 22. The article of claim 21, the article being any one of a kitchen counter-top, a cutting board, a hand-gripping portion of an appliance, a hand-gripping portion of a cabinet, a hand-gripping portion of a drawer, a desk, a table, a light fixture, a light switch, a food package, and a food processing surface.
 23. The article of claim 21, further comprising an adhesive layer disposed between the surface and the antimicrobial coating.
 24. The article of claim 21, wherein the g-C₃N₄ composition of the antimicrobial coating generates reactive oxygen species when irradiated with ultraviolet (UV) or visible light in the presence of oxygen or water.
 25. The article of claim 21, wherein the g-C₃N₄ composition of the antimicrobial coating photocatalytically inactivates or degrades one or more of a protozoan, a eukaryotic parasite, an algal pathogen, a bacterium, a fungus, a prion, and a virus when irradiated with ultraviolet (UV) or visible light in the presence of oxygen or water. 